U.S. patent application number 15/510729 was filed with the patent office on 2018-02-15 for composition comprising a hydrogel and pesticides.
The applicant listed for this patent is NOVIOPONICS B.V.. Invention is credited to Johannes Hendrikus Leonardus HANSSEN, Zhou LUDAN, Robert TWEEHUYSEN.
Application Number | 20180042223 15/510729 |
Document ID | / |
Family ID | 51541002 |
Filed Date | 2018-02-15 |
United States Patent
Application |
20180042223 |
Kind Code |
A1 |
LUDAN; Zhou ; et
al. |
February 15, 2018 |
COMPOSITION COMPRISING A HYDROGEL AND PESTICIDES
Abstract
A composition including at least one pesticide and at least one
thermoreversible hydrogel having a gelling temperature, wherein at
a temperature above the gelling temperature the thermoreversible
gel is gelled, and at a temperature below the gelling temperature
the thermoreversible gel is a liquid. The pesticide is preferably a
herbicide, an insecticide, a fungicide or a bactericide. A process
for the treatment of plants with this composition, the use of the
composition for the treatment of plants and plants including the
composition.
Inventors: |
LUDAN; Zhou; (Nijmegen,
NL) ; HANSSEN; Johannes Hendrikus Leonardus;
(Nijmegen, NL) ; TWEEHUYSEN; Robert; (Nijmegen,
NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
NOVIOPONICS B.V. |
Sittard |
|
NL |
|
|
Family ID: |
51541002 |
Appl. No.: |
15/510729 |
Filed: |
September 15, 2015 |
PCT Filed: |
September 15, 2015 |
PCT NO: |
PCT/EP2015/071143 |
371 Date: |
March 13, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N 25/10 20130101;
A01N 43/12 20130101; A01N 25/24 20130101; A01N 25/04 20130101; A01N
43/12 20130101; A01N 43/12 20130101; A01N 25/10 20130101; A01N
25/24 20130101 |
International
Class: |
A01N 25/04 20060101
A01N025/04; A01N 25/24 20060101 A01N025/24; A01N 43/12 20060101
A01N043/12 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 15, 2014 |
EP |
14184788.9 |
Claims
1. A composition, comprising: at least one pesticide and at least
one thermoreversible hydrogel having a gelling temperature, wherein
at a temperature above the gelling temperature the thermoreversible
hydrogel is gelled, and at a temperature below the gelling
temperature the thermoreversible hydrogel is a liquid.
2. The composition according to claim 1, wherein the pesticide is a
herbicide, an insecticide, a fungicide, a bactericide, an insect
growth regulator, a nematicide, a termiticide, a molluscicide, an
antimicrobial, a disinfectant or a sanitizer.
3. The composition according to claim 1, wherein the composition
has a storage modulus G'.sub.10 at a polymer concentration of 3
mg/ml below 3 Pa measured at a temperature of 10.degree. C.,
determined with a stress-controlled rheometer (Discovery HR-1, TA
Instruments) in an aluminum parallel plate geometry (40 mm
diameter) with a gap of 500 .mu.m in a temperature-controlled
environment.
4. The composition according to claim 1, wherein the composition
has a modulus G'.sub.30 at a polymer concentration of 3 mg/ml of at
least 20 Pa measured at a temperature of 30.degree. C., determined
with a stress-controlled rheometer (Discovery HR-1, TA Instruments)
in an aluminum parallel plate geometry (40 mm diameter) with a gap
of 500 .mu.m in a temperature-controlled environment.
5. The composition according to claim 1, wherein the
thermoreversible hydrogel comprises water and a polymeric
compound.
6. The composition according to claim 5, wherein the polymeric
compound comprises a oligo(alkylene glycol) functionalized
polyisocyanopeptide.
7. The composition according to claim 6, wherein the alkylene
glycol is ethylene glycol and oligo is at least 3.
8. The composition according to claim 5, wherein the
thermoreversible hydrogel comprises 0.01 to 1 wt % of the polymeric
compound based on the total weight of the hydrogel.
9. The composition according to claim 1, wherein the concentration
of the pesticide in the composition is 0.0001-5.0 wt % based on the
total weight of the composition.
10. A process for the treatment of plants or plant parts comprising
the steps of: a) providing a composition comprising a polymer and
optionally a pesticide at a temperature between 0 and 10.degree.
C., and wherein the composition has a gelling temperature where it
changes from a liquid state into a gel state, wherein the gelling
temperature is between 12 and 25.degree. C.; b) Providing a plant
having a temperature above the gelling temperature of the
composition; c) Applying the composition onto the plant by way of
brushing, pouring, dripping or spraying, wherein the composition is
applied to the plants plant or plant parts part and the plants
plant or plant parts part are present in an environment with a
temperature above the gelling temperature.
11. The process according to claim 10, wherein the composition is
applied by spraying.
12. (canceled)
13. (canceled)
14. (canceled)
15. The plant or plant part comprising a composition according to
claim 1.
16. The composition of claim 2, wherein the composition has a
storage modulus G'.sub.10 at a polymer concentration of 3 mg/ml
below 3 Pa measured at a temperature of 10.degree. C., determined
with a stress-controlled rheometer (Discovery HR-1, TA Instruments)
in an aluminum parallel plate geometry (40 mm diameter) with a gap
of 500 .mu.m in a temperature-controlled environment; and wherein
the composition has a modulus G.sup.'.sub.30 at a polymer
concentration of 3 mg/ml of at least 20 Pa measured at a
temperature of 30.degree. C., determined with a stress-controlled
rheometer (Discovery HR-1, TA Instruments) in an aluminum parallel
plate geometry (40 mm diameter) with a gap of 500 .mu.m in a
temperature-controlled environment.
17. The composition of claim 16, wherein the thermoreversible
hydrogel comprises water and a polymeric compound; and wherein the
polymeric compound comprises a oligo(alkylene glycol)
functionalized polyisocyanopeptide.
18. The composition of claim 17, wherein the alkylene glycol is
ethylene glycol and oligo is at least 3; wherein the
thermoreversible hydrogel comprises 0.01 to 1 wt % of the polymeric
compound based on the total weight of the hydrogel, and wherein the
concentration of the pesticide in the composition is 0.0001-5.0 wt
% based on the total weight of the composition.
Description
[0001] The invention is directed to a composition comprising a
hydrogel and pesticides, a process for the treatment of plants with
this composition, the use of the composition for the treatment of
plants and plants comprising the composition.
[0002] Pesticide containing compositions for the treatment of
plants are known. The pesticides are usually dispersed in a
water-based medium that is sprayed on plants. The pesticides are
mostly manufactured in concentrated forms by forming salts or
complexes. When the water-based medium is sprayed on the plants a
large part of the water-based medium will drip of the plants and is
directly absorbed by the soil or the substrate. A part of the
water-based medium will remain on the plant. However, this part is,
over time, washed away with the rain or when the plants are watered
by spraying. There is thus only a small amount of the pesticide
that will remain present on the plant. To have an effective
treatment of the plant with the pesticide spraying of the
water-based medium with the pesticide has to be repeated
frequently. A lot of the pesticide is lost to the soil which is
environmentally unfriendly and the soil needs to be cleaned by
purification processes.
[0003] DE102008032537 A1 discloses a viscous fluid for the
treatment of plants to overcome the problem of dripping.
[0004] WO01/30145 discloses hydrogel microbeads. These can be used
to immobilize agricultural chemicals; for example pesticides.
Compositions comprising the microbeads may be sprayable.
[0005] The use of microbeads for the application of pesticides to
plants has the disadvantage that the microbeads will not attach to
the plants and will wash away with rain. Therefore the effect of
the pesticides in the microbeads is not optimal.
[0006] In US2014/0121109 hydrocolloid formulations comprising an
encapsulated 1-methylcyclopropene (a methylene response
manipulation agent) and optionally a pesticide are disclosed. These
formulations are prepared just before spraying the formulation on
plants or plant parts to ensure that the formulation remains
sprayable. Preparation of the formulation just before spraying has
the disadvantage that only small amounts of the formulation can be
prepared at once. Storage tanks for the various components of the
formulation and a mixing device in combination with a backpack
sprayer or a vehicle mounted sprayer are needed for the application
of the formulation on the plants.
[0007] CN103004757 discloses a composition comprising deltamethrin
or cyhalothrin and a temperature sensitive hydrogel. At low
temperature the gel has a high viscosity, while at high temperature
the gel has a much lower viscosity.
[0008] EP0 022 925 discloses a herbicidal composition in the form
of a suspension concentrate. The viscosity of the suspension
changes depending of the temperature: at higher temperature a lower
viscosity is being obtained.
[0009] DE 10 2008 032 537 discloses a herbicidal composition which
has an increased viscosity at 25 celc to stick to the leaves of
plants and to improve weatherability during rain. These
compositions all have an increased viscosity at lower temperature,
and the function seems to be to prevent easy weathering of the
herbicides by rain and spill of herbicides.
[0010] These solutions do not work properly in greenhouses, since
the temperature in greenhouses is generally higher than ambient
temperature. Moreover, the application of the hydrogels is
difficult: either one should try to spray highly viscous
compositions or the compositions should be heated to lower the
viscosity. Spraying heated solutions containing pesticides and
herbicides can easily burn plants and inhibit plant growth.
[0011] There is a need for an improved composition for treatment of
plants, which can be easily applied, shows an increased efficiency
in use of pesticides.
[0012] The object of the invention is to provide an effective
composition and process for treatment of plants with pesticides, to
minimize the amount of pesticide needed, to minimize the spill of
pesticides and therefore reduce the cost of growing plants
especially in greenhouses.
[0013] The invention is characterized by a composition comprising
at least one pesticide and at least one thermoreversible hydrogel
having a gelling temperature, wherein at a temperature above the
gelling temperature the thermoreversible gel is gelled, and at a
temperature below the gelling temperature the thermoreversible gel
is a liquid.
[0014] The compositions according to the invention comprise
thermoreversible hydrogels that give the compositions liquid
behavior at low temperatures (for example between 0 and 10.degree.
C.) and elastic gel behavior at higher temperatures (for example at
a temperature between 20 and 40.degree. C.).
[0015] This has the advantage that the viscosity of the composition
is such that the composition can be sprayed at a low temperature.
The thermoreversible compositions preferably are being used under
circumstances where the temperature of the plants is above the
gelling temperature of the thermoreversible composition. Such
circumstances are present in for example greenhouses.
[0016] After spraying the composition forms a gel on the surface of
the plant or plant parts and thus attaches to and remains on the
plant or plant parts. In this way the drip of the composition
containing pesticide will be extremely decreased.
[0017] A further advantage is that the hydrogel forms a homogenous
gel layer which could cover the hydrophobic plant surface
completely, while this deposition phenomenon will not happen when
hydrophilic water contact the plant. Using of hydrogel could
efficiently increase the contact area of pesticide and plant.
Furthermore the pesticide may show slow release from the gel to the
plant over a prolonged period of time or alternatively will treat
the plant against diseases like for example bacteria, insects and
the like. Frequent treatment of the plant is thus not necessary, or
at least the frequency of the treatments of the plants with
pesticides can be reduced.
[0018] Another advantage is that by the less frequent treatment the
burden on the environment is reduced. Moreover, the costs for the
treatment of plants will be reduced because less of the pesticide
needs to be used, and less treatment of soil or waste water is
needed to clean waste water and soil from pesticide.
[0019] Another advantage is that the hydrogel kills small insects
like spint on plants, thereby increasing the efficiency of the
pesticides and showing a clear synergistic effect with pesticides
in the treatment of plants.
[0020] Thermoreversible Hydrogel
[0021] The thermoreversible hydrogel comprises water and a
polymeric compound. The polymeric compound forms a network wherein
a substantial amount of water is included.
[0022] The hydrogels of the present invention have a gelling
temperature.
[0023] The gelling temperature typically ranges between 12 and
25.degree. C., preferably between 13 and 20.degree. C., or between
14 and 18.degree. C.
[0024] Below the gelling temperature the hydrogel has liquid
behavior and can flow easily out of a container.
[0025] In an embodiment, the low viscosity behavior can be
quantified with a low storage modulus G'.sub.10. G'.sub.10 is
defined as the storage modulus of a composition comprising 3 mg/ml
polymer in water measured at a temperature of 10.degree. C., with
the aid of a rheometer. G'.sub.10 is below 3 Pa, preferably below 2
Pa, more preferably below 1 Pa.
[0026] Above the gelling temperature the hydrogel shows no flow in
a vial tilt test. When a glass vial which contains the gel is
turned upside down, no flow of the gel is observed during 15
seconds observation time. The gelling temperature of the hydrogel
is dependent on the polymer used, the concentration of the polymer
and the molecular weight of the polymer. In an embodiment the high
viscosity behavior, or elastic gel behavior, can be quantified with
and a high G'.sub.30. G'.sub.30 is defined as the storage modulus
of a hydrogel comprising 3 mg/ml polymer in water measured at a
temperature of 30.degree. C., with the aid of a rheometer.
G'.sub.30 is typically above 20 Pa, preferably above 30 Pa, or
between 50 and 1000 Pa, or between 100 and 500 Pa.
[0027] The polymeric compound in the hydrogel can be chosen from
various groups of polymers. The polymeric compound should at least
be partly hydrophilic. Examples of polymeric compounds are
polysaccharides, such as carrageenan and agar-agar, gelatin,
pluronic hydrogel and Poly(N-isopropylacrylamide) (PNIPAm)
hydrogel.
[0028] In one embodiment the polymeric compound is a diblock
copolymer of the formula (1) B-A or a triblock copolymer of the
formula (2) B-A-B or formula (3) A-B-A. In formula (1), (2) and (3)
B stands for a hydrophobic block and A stands for a hydrophilic
block.
[0029] With `hydrophilic block` is meant that the block by itself
has a solubility in water. For example polyalkyleneglycols or
polyethers are hydrophilic blocks. Examples of polyalkyleneglycol
are polypropyleneglycol (PPG) or polyethyleneglycol (PEG)
[0030] With `hydrophobic block` is meant that the block by itself
has a very low solubility in water. Examples of hydrophobic blocks
are polyester blocks, polyester-amide blocks, polylactide blocks
(PLA), polyglycolide blocks (PGA), poly (lactide-co-glycolide)
(PLGA) blocks, polycaprolactone blocks and polydioxanon blocks
[0031] In the block copolymers according to formula (1), (2) and
(3) A preferably is a linear hydrophilic block, for example a
linear poly-(ethylene glycol) block (PEG block).
[0032] In the block copolymers according to formula (1), (2) and
(3) B preferably is a linear hydrophobic block.
[0033] Generally, the number average molecular weight (Mn) of the
blocks in the block copolymer according to formula (1), (2) and (3)
is at least 1000 Da, for example at least 1500 Da and/or preferably
at most 8000 Da, for example at most 5000 Da. The number average
molecular weight as used herein is defined as the number average
molecular weight as determined using .sup.1H nuclear magnetic
resonance.
[0034] In another, and preferred, embodiment the polymeric compound
is chosen from oligo(alkylene glycol) functionalized
polyisocyanopeptides. Oligo(alkylene glycol) functionalized
polyisocyanopeptides are, for example, described by Hase et al.
Chem.-Asian J. 2007, 2, 755-763, Kitto et al. J. Mater Chem 2008,
18, 5615-5624 and in WO-2011007012.
[0035] These polymeric compounds comprise a poly(isocyanopeptide)
backbone functionalized with oligo(alkylene glycol) chains that are
grafted onto the backbone and can be represented by the following
formula:
##STR00001##
[0036] In the formula m represents the number of isocyanopeptides
and can be an integer from 1-100,000 and n represents the number of
alkylene glycol units and can be an integer from 1-10. In the
formula two units of alanine are used as an example of the peptide
part, and ethylene glycol is used as an example of alkylene
glycol.
[0037] The isocyanopeptide backbone can, for example, comprise the
amino acids alanine, arginine, asparagine, aspartic acid, cysteine,
glutamic acid, glutamine, glycine, histidine, isoleucine, leucine,
lysine, methionine, phenylalanine, proline, serine, threonine,
thryptophan, tyrosine and valine.
[0038] The oligo(alkylene glycol) chains may be linear, branched or
dendronized. Preferably, the oligo(alkylene glycol) chain is
linear.
[0039] In oligo(alkylene glycol) oligo refers to 1-10 alkylene
glycol repeating units. Examples of suitable alkylene glycols are
ethylene, propylene, butylene or pentylene glycol. Preferably, the
alkylene glycol is ethylene glycol.
[0040] Examples of suitable alkylene glycols are ethylene-,
propylene-, butylene- or pentylene glycol. Preferably the alkylene
glycol is ethylene glycol.
[0041] Advantageous oligoethyleneglycol units are depicted below.
In general, the term oligo refers to a number<10.
##STR00002##
[0042] Preferably the isocyanopeptides are substituted with at
least 3 ethylene glycol units to lead to water soluble materials
after polymerization.
[0043] The poly(isocyanopeptide) can be a homopolymer comprising
one type of isocyanopeptide functionalized with one type of linear
or non-linear oligo(alkylene glycol). The poly(isocyanopeptide) can
also be a copolymer comprising two or more types of isocyanopeptide
and/or two or more types of linear or non-linear oligo(alkylene
glycol)s.
[0044] The polymerization is preferably performed in the presence
of an apolar solvent. Suitable apolar solvents may be selected from
the group consisting of saturated hydrocarbon solvents and aromatic
hydrocarbon solvents or mixtures thereof. Examples of apolar
solvents are pentane, hexane, heptane, 2-methylbutane,
2-methylhexane, cyclohexane, and toluene, benzene xylenes or
mixtures thereof. Preferably toluene is used in the polymerization.
Preferably toluene is chosen for the polymerization process of
oligo(ethylene glycol) isocyanopeptides where the oligo(ethylene
glycol) part contains at least three ethylene glycol units.
[0045] Preferably the polymerization is carried out in the presence
of a catalyst. The catalyst is preferably a nickel(II) salt.
Example of Ni(II) salts are nickel(II) halides (e.g. nickel(II)
chloride), nickel(II) perchlorate or
tetrakis-(tertbutylisocyanide)nickel(II) perchlorate.
[0046] Other complexes and nickel salts might be used provided that
they are soluble in the polymerization medium or initially
dissolved in an adequate solvent which is miscible in the
polymerization medium. General references describing some catalytic
systems that may be used to polymerize the oligo(alkylene
glycol)isocyanopeptides may be found in Suginome M.; Ito Y; Adv
Polym SC1 2004, 171 , 77-136; Nolte R. J. M.; Chem. Soc. Rev. 1994,
23(1), 11-19)]
[0047] Preferably the monomer concentration is chosen above 30
mmol/L and the catalyst/monomer ratio chosen between 1/100 and 1/10
000. Lowering the amount of nickel(II) (catalyst/monomer ratio
below 1/1000) permits the preparation of materials exhibiting a
substantial degree of polymerization [mean DP>500], which is
desired for subsequent application of the polymers as
macro-hydrogelators.
[0048] In a representative example, a millimolar solution of
monomer in a nonpolar organic solvent or mixture of solvents is
added to a nickel (II) catalyst dissolved in a polar solvent in a
molar ratio of 1:50 up to 1:100,000 catalyst to monomer. In a
sealed environment the mixture is vigorously stirred for 2 to 24
hrs. Once completed, the reaction mixture is evaporated and the
crude product is dissolved in organic solvents and precipitated in
diethylether or similar non-compatible organic solvents, giving the
desired product.
[0049] Thermoreversible hydrogels are, for example, disclosed in
WO2001/82970, WO2011/007012 and WO2012/131106.
[0050] The thermoreversible hydrogel can comprise 0.01 to 1 wt % of
the polymeric compound based on the total weight of the hydrogel.
Preferably, the amount of polymeric compound is 0.05 to 0.7 wt %,
more preferably 0.1 to 0.5 wt %.
[0051] The amount of water in the hydrogel is preferably between 99
to 99.99 wt %, preferably, 99.3 to 99.95 wt %, more preferably 99.5
to 99.9 wt %.
[0052] An advantage of the use of oligo(alkylene glycol)
functionalized polyisocyanopeptides is the low concentration of
polymer needed to make a hydrogel with a very high viscosity.
Preferably the concentration of polymer ranges between 0.01 and 1
wt %, more preferably between 0.05 and 0.7 wt % of polymer relative
to the total of the composition.
[0053] After the formation of the hydrogel the hydrogel has a
certain viscosity and storage modulus G'. The viscosity and modulus
are dependent on the amount of polymeric compound in the hydrogel,
the molecular weight of the polymer and on the temperature of the
hydrogel.
[0054] The compositions comprising the hydrogel and at least one
pesticide have the unique property that at low temperatures they
show a low viscosity and low storage modulus G', whereas at higher
temperatures the compositions form an elastic gel, having a higher
storage modulus G' . Preferably, the composition has a storage
modulus G'.sub.10 at 10.degree. C. below 3 Pa, preferably below 2
Pa or below 1 Pa, measured at a concentration of 3 mg polymer/ml
water. At a temperature of 30.degree. C. the storage modulus of the
G'.sub.30 is typically above 10 Pa, or above 20 Pa, or between 30
and 1000 Pa.
[0055] The concentration of the pesticide in the composition is 0-7
wt %, preferably 0.0001-5.0 wt % based on the total weight of the
composition.
[0056] Pesticide
[0057] The composition according to the invention preferably
comprises a pesticide. Pesticides are substances meant for
attracting, seducing, destroying, or mitigating any pest. The most
common use of pesticides is as plant protection products (also
known as crop protection products), which in general protect plants
from damaging influences such as weeds, plant diseases or insects.
The term pesticide includes all of the following: herbicide,
insecticide, insect growth regulator, nematicide, termiticide,
molluscicide, piscicide, avicide, rodenticide, predacide,
bactericide, insect repellent, animal repellent, antimicrobial,
fungicide, disinfectant, and sanitizer.
[0058] Preferably the pesticide is a herbicide, an insecticide, a
fungicide, a bactericide an insect growth regulator, a nematicide,
a termiticide, a molluscicide, an antimicrobial, a disinfectant or
a sanitizer.
[0059] In general, a pesticide is a chemical or biological agent
(such as a virus, bacterium, antimicrobial, or disinfectant) that
deters, incapacitates, kills, or otherwise discourages pests.
Target pests can include insects, plant pathogens, weeds, mollusks,
birds, mammals, fish, nematodes (roundworms), and microbes that
destroy property, cause nuisance, or spread disease, or are disease
vectors.
[0060] Herbicide
[0061] The composition according to the invention can comprise a
herbicide. Herbicides are also known as weed killers and are used
to kill unwanted plants.
[0062] Examples of herbicides are 2,4-dichlorophenoxyacetic acid
(2,4-D), aminopyralid, atrazine, clethodim, chlorimuron,
chlorsulfuron, clopyralid, dicamba, diclofopmethyl, glufosinate
ammonium, fluazifop, fluroxyyr, glyphosate, imazapyr, imazapic,
imazamox, imazaquin, imazethapyr, linuron,metsulfuron, metolachlor,
paraquat, pendimethalin, picloram, primisulfuron, quizalofopethyl,
rimsulfuron, sodium chlorate, sethoxydim, sulfometuron,
tralkoxydim, triasulfuron, 2,4,5-trichlorophenoxyacetic acid
(2,4,5-T) and triclopyr.
[0063] Insecticide
[0064] The composition according to the invention can comprise an
insecticide. Insecticides are used to kill insects.
[0065] Examples of insecticides are organochlorides, such as DDT;
organophosphates and carbamates; pyrethroids, such as imidacloprid;
neonicotinoids; ryanoids, such as rynaxypyr; insect growth
regulators; plant-produced insecticides and bacterial
insecticides.
[0066] Fungicide
[0067] The composition according to the invention can comprise a
fungicide. Fungicides are used to kill or inhibit fungi or fungal
spores.
[0068] Many fungicides comprise sulfur. Other examples of
fungicides are cinnamaldehyde, citronella oil, jojoba oil,
monocerin, neem oil, oregano oil, rosemary oil, the bacterium
Bacillus subtilis, and the beneficial fungus Ulocladium
oudemansii.
[0069] Bactericide
[0070] The composition according to the invention can comprise a
bactericide. Bactericides are used to kill bacteria. Apart from
bactericides bacteriostatics can also be used.
[0071] Bacteriostatics are compounds that slow the growth or
reproduction of bacteria.
[0072] Bactericides can be disinfectants, antiseptics, or
antibiotics.
[0073] Examples of bactericides are hypochlorites, chloramines,
dichloroisocyanurate, chlorine dioxide, povidone-iodine, Lugol's
solution, ethanol, 1-propanol, 2-propanol, 2-phenoxyethanol,
1-phenoxypropanol, 2-phenoxypropanol, phenol, cresol,
hexachlorophene, triclosan, trichlorophenol, tribromophenol,
pentachlorophenol, dibromol, quaternary ammonium compounds (for
example benzalkonium chloride, cetyl trimethylammonium bromide,
didecyldimethylammonium chloride, cetylpyridinium chloride,
benzethonium chloride, chlorhexidine, glucoprotamine, octenidine
dihydrochloride), ozone, permanganate solutions, silver, silver
nitrate, mercury chloride, phenylmercury salts, copper sulfate,
copper oxide, phosphoric acid, nitric acid, sulfuric acid,
amidosulfuric acid, toluenesulfonic acid, sorbic acid, benzoic
acid, lactic acid and salicylic acid, sodium hydroxide, potassium
hydroxide and calcium hydroxides.
[0074] Use
[0075] The composition according to the invention can be used to
treat various objects that need to be protected against insects and
deceases and is normally treated with a pesticide. In one
embodiment of the invention, the thermoreversible hydrogel can be
used without the use of pesticides, for example in the protection
of plants from Glasshouse red spider mite--Tetranychus urticae. In
a preferred embodiment of the invention, the composition contains a
thermoreversible gel and at least one pesticide.
[0076] Examples of these objects are constructions, such as houses
or other buildings and in general surfaces in buildings; plants The
composition can, for example, be applied by brushing, pouring,
dripping and spraying. Preferably, the composition is used for the
treatment of plants or plant parts in horticulture and
agriculture.
[0077] The invention is also directed to the use of a
thermoreversible hydrogel for the treatment of plants or plant
parts.
[0078] The invention is further directed to the use of a
polyisocyanopeptide functionalized with an oligo(alkylene glycol)
for the treatment of plants or plant parts.
[0079] Process
[0080] The invention is further directed to a process for the
treatment of plants or plant parts comprising the steps of [0081]
a) Providing a composition comprising a polymer and optionally a
pesticide at a temperature between 0 and 10.degree. C., and wherein
the composition has a gelling temperature above 10.degree. C. where
it changes from a liquid state into a gel state [0082] b) Providing
a plant having a temperature above the gelling temperature of the
composition [0083] c) Applying the composition onto the plant by
way of brushing, pouring, dripping or spraying.
[0084] Because of the low viscosity and low modulus of the
composition at low temperatures the composition is liquid when the
composition is applied to the plants. The environments of the
plants and the plant or plant parts itself have a higher
temperature (for example above 18.degree. C., preferably in the
range between 20 and 40.degree. C., or between 22 and 39.degree.
C., or between 25 and 38.degree. C.) that warms the composition
such that the composition forms a gel. The gel is preferably formed
on the outside of the plant or plant parts during or directly after
application. Warming up of the composition can occur faster when
the composition is finely divided. Therefore, the composition is
preferably applied by spraying.
[0085] After growth of the plants, the hydrogel can be removed from
the crop or any fruits by simply cooling the plants, or spraying
with cold water. The hydrogel according to the invention is
thermoreversible, which means that upon cooling the hydrogel
becomes liquid again, and can be removed from the plants. This
provides an additional advantage over any known method in the
art.
[0086] Plant
[0087] The invention is further directed to a plant or plant part
comprising the composition according to the invention.
FIGURES
[0088] FIG. 1 shows the dead percentage of spider on paprika plants
(example 1).
[0089] FIG. 2 shows the overview of coverage pattern of water,
water+Motto.RTM., water+Hasten.TM. and water+NovioHelix.
Tinopal.RTM. was used to visualize the coverage pattern and gives
blue color under UV-light.
[0090] FIG. 3 shows the coverage pattern of water versus
NovioHelix. The leaf surface was treated with water or NovioHelix
A) under normal light and B) under UV-light.
[0091] FIG. 4 shows the drip-off after applying pesticide with
water, water with Motto.RTM., water with Hasten.TM. and water with
NovioHelix. The drip-off of water was set to 100%. Adjuvant
Motto.RTM. has no influence on drip-off. Hasten.TM. decreases 4%
drip-off. NovioHelix decreases 20% drip-off in comparison to
water.
EXPERIMENTS AND EXAMPLES
[0092] Synthesis and Polymerization of Temperature Sensitive
Hydrogels.
[0093] The synthetic temperature-sensitive hydrogels (PIC
hydrogels) have been synthesized from polyisocyanopeptides grafted
with oligo(ethylene glycol) side chains. To obtain these polymers,
polyisocyanopeptides where synthesized by polymerization of
methoxy-functionalized monomers.
[0094] Polymerization of triethylene glycol functionalized
isocyano-(D)-alanyl-(L)-alanine monomer was catalysed by the
addition of nickel(II), Ni(Cl2O4)2*6H2O, with a molar ratio of
1:4000. This resulted in the polymerization of the methoxy
monomer.
[0095] Triethylene glycol functionalized
isocyano-(D)-alanyl-(L)-alanine monomer is represented by the
following formula:
##STR00003##
[0096] Monomer Purification
[0097]
2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethyl-(L)alaninyl-(D)-isocya-
noalanine (3EG) monomer was obtained from Chiralix. Previous
analysis of 3EG Chiralix monomer by TLC and NMR showed some minor
degradation or racemization peaks. 12 g of 3EG monomer from
Chiralix were purified by chromatographic column (75% DCM, 25%
AcCN).
[0098] Polymerization Reaction
##STR00004##
[0099] In a 500 mL round bottom flask with 10.1 g of purified 3EG
Chiralix monomer were dissolved in 200 mL of freshly distilled
toluene. 100 mL of Ni(OCl.sub.4).sub.2 catalyst solution (2.93 mM,
25% EtOH and 75% Toluene. First catalyst was dissolved in EtOH
followed by subsequent dilution with toluene) was prepared. 0.996
mL of Ni(OCl.sub.4).sub.2 catalyst solution was added in one
portion to the monomer solution under vigorous stirring for 1
minute after which, stirring was decreased to a moderate level and
the reaction allowed to proceed at r.t. for 5 days. After 1 day,
reaction the mixture became orange, with a high viscosity at which
point the stirring slowed to a gentle agitation. After 4 days IR
confirmed reaction was completed. There was not CN at peak at
.about.2140 cm-1, indicating complete consumption of the 3EG
monomer.
[0100] Precipitation Process (Repeated 3 Times)
[0101] The resulting orange reaction mixture was taken up in 300 mL
of DCM and stirred with an overhead mechanical stirrer to ensure a
homogeneous solution. It has been observed in previous experiments
that stirring using a magnetic stirrer does not result in a
homogenous solution. After 2 h of stirring gently reaction mixture
was completely dissolved. A 200 mL portion of the solution in a 200
mL glass syringe was added the mixture slowly drop wise into a 5 L
Erlenmeyer containing 4 L of diethyl ether under vigorously
stirring. The entire 500 mL of the reaction mixture dissolved in
DCM was precipitated in a total of 8 L of diisopropyleter. The
precipitate was kept under stirring for 30 minutes and then
filtered in three portions into three Buchner funnels. When all
precipitate was added, filtrate was kept in the Buchner funnel
(Which was connected to vacuum line) and the precipitate was dried
over night. The polymer was removed from the filter paper, placed
into a 500 mL round bottom flask and dried first under reduced
pressure for 4 h and then using a high vacuum line overnight until
all the solvent was evaporated (No odor, constant weight) the
polymer was obtained as an off orange powder (9.2 g, 91% yield).
The polymer, it was kept in a 500 mL round bottom flask under argon
atmosphere at at -18 degrees.
[0102] Characterization.
[0103] Rheological measurements were carried out with a
stress-controlled rheometer (Discovery HR-1, TA Instruments) in an
aluminium parallel plate geometry (40 mm diameter) with a gap of
500 .mu.m in a temperature-controlled environment. To probe the
linear regime (G0), the sample was heated to the desired
temperature, and after a short waiting period for equilibration the
complex modulus G* was determined by applying an oscillating
deformation of amplitude .gamma.=0.01 in a frequency sweep of
.omega.=10-0.1 Hz. The nonlinear regime was studied using a
pre-stress protocol, where the sample, at the desired temperature
was subjected to a constant stress .sigma..sub.0 with a small
oscillatory stress superposed, also at .omega.=10-0.1 Hz. In the
pre-stress protocol that we use to probe the nonlinear mechanical
regime, we apply a constant stress to the material. We did not find
relaxation processes in the materials, even at high stresses.
[0104] The modulus of a viscoelastic material is called the complex
modulus (G*) and consists of both the solid and liquid contribution
as shown in the equation below where G' is the storage modulus (the
solid contribution) and G'' is the loss modules (liquid
contribution).
G*= ((G')2+(G'')2)
[0105] Stiffness of the hydrogels is determined by the solid
component (G') at well defined temperatures of 10 and 30.degree.
C.
[0106] To investigate the thermo responsive gel properties and to
determine G'.sub.10 and G'.sub.30 the rheology of a sample
comprising 3 mg/ml polymer in water was measured with a temperature
ramp. Rheology measurements of the polymer used in the examples
indicates a gelation point of 16.degree. C. and a G'.sub.10 of 1 Pa
and G'.sub.30 of 100 Pa at 30.degree. C. Viscosity average
molecular weight (Mv): 450 KDa.
EXAMPLE 1
Effectiveness of Use of Hydrogel
[0107] The objective of this experiment is to examine the
effectiveness of pesticides with the use of NovioHelix as a
pesticide adjuvant.
[0108] NovioHelix is the polymer of the triethylene glycol
functionalized isocyano-(D)-alanyl-(L)-alanine monomer, represented
by the formula:
##STR00005##
[0109] Materials and Methods:
[0110] Paprika plants infected with spider mite (Tetranychus
uricae) were used as experiment samples. All paprika (.+-.20cm)
were artificially infected with spiders 5 days before the
experiments. The insecticide Spiromesifen (Spiromesifen, 240 g/l,
Oberon) was used to against spiders. Noviohelix (3 mg/mL) was used
as an adjuvant. All samples were applied with pesticide until `till
run off` (the first droplet of a composition fall off the leave).
The effectiveness of Spiromesifen either with or without NovioHelix
was determined based on the dead percentage of spiders after
treatment. The spiders both in mature and immature phases were
counted before and at day 5 after experiment.
[0111] Table 1 gives an overview of the groups were made for this
experiment:
TABLE-US-00001 Group Condition 1 without any treatment 2 Water 3
Noviohelix .RTM. only 4 Spiromesifen 5 spiromesfen + Noviohelix
.RTM.
[0112] Result:
[0113] Table 2 and FIG. 1 show the dead percentage of spider at day
5 after treatment. Water has a negative influence on the survival
of spider. 12.7% death of spider has been observed after applying
water. Noviohelix.RTM. without any insecticide shows 47.6% death.
Spiromesifen gives more dead percentage with adding NovioHelix
(97.7% death of spider) in comparison with Spiomesifen only (84.8%
death of spider).
TABLE-US-00002 TABLE 2 The dead percentage at day 5 after
treatment. Groups % dead 1. without 18.8 2. water 12.7 3. hydrogel
47.6 4. Spiromesifen 84.8 5. Spiromesifen + Noviohelix 97.7
[0114] Conclusion:
[0115] The experiment shows that use of a hydrogel containing
NovioHelix.RTM. as a new pesticide adjuvant increases the
effectiveness of Spiromesifen against spider mite on paprika
plants. NovioHelix.RTM. hydrogel surprisingly has a negative
influence on the survival of spiders, even in the absence of any
pesticide.
EXAMPLE 2
Coverage of Plants Leafs with Noviohelix Hydrogel
[0116] The objective of this study is to determine the coverage
pattern of plants when they are treated with different mixtures
containing water, a composition having water and ??? and a
composition comprising a hydrogel having Noviohelix as an
adjuvant.
[0117] Materials and Methods:
[0118] Motto.RTM. is a concentrate of 263 g/l sugarderivative and
modified fatty acid amine, used in combination with pesticides to
improve the contact between pesticide and plant and the improvement
of the uptake of the pesticide by the plants.
[0119] Hasten.TM., is a blend comprising esterified rape oil and an
emulsifier system, to improve the contact between pesticides,
insects and plant leafs and to improve the working of the
pesticides against insects.
[0120] Paprika plants were used as experiment samples. The coverage
of the plants was evaluated with water only, water with
Motto.RTM.(Motto.RTM. 0.03%, BASF, Germany), water with Hasten
(Hasten.TM.,0.25%, Surfaplus BV, The Netherlands) and water with
Noviohelix (3 mg/ml). All leaves were applied with the same amount
of liquid mixture. Tinopal.RTM. was added in all of these groups to
visualize the coverage pattern. Pictures were made under UV-light.
The percentage of the coverage was determined with program called
Image J.
[0121] Results:
[0122] FIG. 2 gives an overview of the coverage pattern of water,
water with Motto.RTM., water with Hasten.TM. and water with
NovioHelix. NovioHelix shows obviously better coverage compared to
water or adjuvants Motto.RTM. and Hasten.TM.. Next to this, the
coverage pattern of water versus water with NovioHelix is shown in
FIG. 3.
[0123] The coverage percentage after adding NovioHelix (90.4%) is
significantly higher compared to water only (46.4%) or Motto.RTM.
(49.6%) and Hasten.TM. (19.2%).
TABLE-US-00003 TABLE 3 The coverage percentage. water + water +
Group water water + Motto .RTM. Hasten .TM. NovioHelix The
percentage of 46.4 49.6 19.2 90.4 coverage in % SD in % 2.1 1.1 1.6
1.4
[0124] Conclusion:
[0125] NovioHelix enhances the coverage of water extremely and
gives much better cover compared to Motto.RTM. or Hasten.TM.. This
means that a more effective coverage of plants with a composition
with a pesticide can be obtained, and a better protection of the
paprika plants against attack of insects.
EXAMPLE 3
Drip-Off of Noviohelix
[0126] The aim of this study is to determine the reduction of
drip-off with use of NovioHelix.
[0127] Materials and Methods:
[0128] Paprika plants (.+-.20 cm) were used as experiment samples.
The drip-off after adding NovioHelix in water was compared to water
only, water with Motto.RTM. and water with Hasten.TM.. All paprika
groups (5 samples/group) were applied with 100 ml liquid mixture
with the same applying equipment and condition. Each paprika sample
was placed in a plastic container during the experiment and will be
removed after. The container was used to catch the drip-off. The
difference in weight of container before and after liquid applying
was indicated as drip-off.
[0129] Results:
[0130] Motto.RTM. shows no obvious difference in drip-off compared
to water. Hasten.TM.shows slightly less drip-off. NovioHelix
decreases 20% drip-off compared to water (table 4 and FIG. 4).
TABLE-US-00004 TABLE 4 The drip-off of water, water with Motto
.RTM., water with Hasten .TM. and water with NovioHelix. Groups
drip-off SD water 100% 0 water + Motto .RTM. 100% 11% water +
Hasten .TM. 96% 8% water + NovioHelix 80% 7%
[0131] Conclusion:
[0132] NovioHelix reduces the pesticide drip off with 20% compared
to water on paprika plants. NovioHelix gives better effect on drip
off compared to Motto.RTM. and Hasten.TM. on paprika plants.
* * * * *